Nanofibrous electrocatalyst including nanofibrous continuous network of graphitic nanofibers having embedded catalytically active metal moieties

ABSTRACT

A nanofibrous catalyst and method of manufacture. A precursor solution of a transition metal based material is formed into a plurality of interconnected nanofibers by electro-spinning the precursor solution with the nanofibers converted to a catalytically active material by a heat treatment. Selected subsequent treatments can enhance catalytic activity.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This application is a Divisional of U.S. application Ser. No.13/630,930, filed Sep. 28, 2012, incorporated herein by reference in itsentirety.

GOVERNMENT INTEREST

This invention was made with government support under Contract No.DE-AC02-06CH11357 awarded by the United States Department of Energy toUChicago Argonne, LLC, operator of Argonne National Laboratory. Thegovernment has certain rights in the invention.

FIELD OF THE INVENTION

The present invention relates generally to the field of catalysts. Moreparticularly the invention relates to nanofibrous electrocatalysts andmethods of manufacture. In addition, the invention relates to a fabriccatalyst and method of preparation where the fibers have nanometerdimensions providing enhanced catalytic performance, particularly forproton exchange membrane fuel cell and lithium-air battery applications.

BACKGROUND OF THE INVENTION

The current invention discloses a method of preparing a fabric electrodecatalyst with diameters of the fibers having nanometer dimensions. Suchnanofiber catalysts can be used in proton exchange membrane fuel cell(PEMFC) and Li-air battery (LAB) applications.

A proton exchange membrane cell (“PEMFC”) is an effective device forenergy conversion applications. A PEMFC can convert chemical energy toelectric energy through the electro-catalytic reactions. The PEMFCoperates at a relatively low temperature with the gas phase hydrogenused as fuel and oxygen (air) used as an oxidant. Due to its highconversion efficiency, low noise and low emissions, a PEMFC is deemed tohave high potential in the areas of automobile and distributed powergeneration.

At the core of a PEMFC is the membrane electrode assembly (“MEA”) whichincludes an anode, a cathode and a polymer electrolyte layer disposedtherebetween. At the surface of the anode, hydrogen is oxidized toprotons through an electro-catalytic process,H₂→2H⁺+2e′  (1)The protons thus produced are transported to the cathode side of thecell through a proton conductive membrane. At the surface of thecathode, oxygen is electro-catalytically reduced and subsequently reactswith protons in accordance with equation (1) to form water,O₂+4e ⁻−4H⁺→2H₂O  (2)Equation (2) is also known as the oxygen reduction reaction (“ORR”). Thereactions of Equations (1) and (2) occur on the surface of electrodecatalysts. At present, the most effective catalyst for these reactionsare made of platinum supported on amorphous carbon. A typical Pt loadingon MEA surface ranges from 0.2 mg/cm² to 0.4 mg/cm². Since platinum is aprecious metal with very limited supply, its usage adds a significantcost to a PEMFC system. Other platinum group metals (“PGMs”), such asPd, Rh, Ru, are also being evaluated as a replacement for Pt. They too,suffer from the same issues as high cost and limited reserves. There isthus a strong need to find low cost materials as non-PGM catalysts toreplace the usage of PGM materials to lower the overall cost of fuelcell systems.

A rechargeable Li-air battery represents another importantelectrochemical device that has high energy storage density andpotentially high conversion efficiency. A LAB can be generally dividedinto three key components; an anode and a cathode separated by anelectrolyte layer or membrane. The anode is made of lithium metal whichexchanges between the ionic and metallic states during thedischarge/charge processes. The electrochemical process occurring at theanode surface can be described simply by the following reversibleequation:Li→Li⁺ +e  (3)The Li⁺ ion thus formed will be shuttled back and forth between and theanode and cathode through a lithium ion conducting electrolyte membraneduring the discharging-charging cycle. For an aprotic LAB, the oxygen iselectro-catalytically reduced to oxide ions during the discharging cycleand re-oxidized back to gaseous O₂ during the charging cycle (oxygenevolution reaction, or “OER”) at the cathode catalyst surface through areversible interaction with Li⁺ ion according to the following reaction:O₂+2e ⁻+2Li⁺↔Li₂O₂  (4)The equation (4) is generally called as the oxygen reduction reaction(ORR) for the forward reactions and oxygen evolution reaction (OER) forthe reverse reactions, respectively.

At present, there exist a number of technical challenges facing LABdevelopment. The first is the electric energy efficiency for thedischarge-charge cycle. The discharging voltage of a LAB is directlyaffected by the kinetic barrier therefore the overpotential of theforward reaction in (4). Similarly, the barrier of the reverse reactionof Equation (4) influences the charging overpotential, and therefore thevoltage. An effective catalyst in the LAB cathode can decrease bothdischarging and charging overpotentials, thereby improving the electricconversion efficiency. The current cathode catalysts for LAB aretypically made of metal oxides supported on high surface area amorphouscarbons. Such carbons can often be electrochemically oxidized undercathode environment. Furthermore, porous amorphous carbons often limitthe interaction between oxygen and the electrolyte with the catalyst dueto lack of sufficient triple-phase boundary and poor mass transfer.Consequently, there is a substantial need for an improved catalyst toremedy these problems.

In typical PEMFC applications, a cathodic oxygen reduction reaction,such as that described by Equation 2 provide hereinbefore, typicallyoccurs at the catalyst surface of platinum supported by amorphouscarbons, such as Pt/C. Few catalyst metals were found to have acomparable catalytic efficiency to that of platinum for the ORR. Thosefound with similar catalytic activity usually are in the precious groupmetals (“PGM”), such as Pd, Rh, Ir, Ru, in addition to Pt. The PGMsgenerally carry a high price due to limited reserves worldwide. The useof PGMs for an electrochemical device, such as a fuel cell, addsignificant cost to the system which therefore creates major barriersfor commercialization. It is thus highly desirable to find low costalternatives to PGMs as the electrode catalyst for fuel cell and similarelectrocatalytic applications.

There have been many attempts to identify the replacements for PGMs,mainly through materials involving the transition metal compounds. Forexample, it has been known that the molecules containing a macrocyclicstructure with an iron or cobalt ion coordinated by nitrogen from thefour surrounding pyrrolic rings have the catalytic activity to captureand to reduce molecular oxygen. It has been demonstrated in the priorart that ORR catalytic activity can be further improved for such systemscontaining coordinated FeN₄ and CoN₄ macrocycles if they have beenheat-treated. Recent prior art experiments have shown a similar methodof making amorphous carbon based catalyst with good ORR activity bymixing macromolecules with FeN₄ group and carbonaceous material orsynthetic carbon support, followed by high temperature treatment in thegas mixture of ammonia, hydrogen and argon. A prior art US patent hasdiscussed a method of preparing non-PGM catalyst by incorporatingtransition metals to heteroatomic polymers in the polymer/carboncomposite, and also this art considered a method to improve the activityof polymer/carbon composite by heat-treating the composite at elevatedtemperature in an inert atmosphere of nitrogen. Other prior art hasreported another route of making porous non-PGM electrode catalyst usingmetal-organic framework material as precursors. Such an approach waslater expanded by using an organometallic complex impregnated MOFsystem. The electrode catalysts prepared through these prior methods aregenerally in the form of powdered materials. To compensate for therelativity low catalytic activity on single catalytic site in comparisonwith that of precious metals, more catalyst materials are generallyrequired to prepare fuel cell membrane electrode of the same geometricarea. More materials often result in a thicker cathode and hence poorermass transfer, which is undesirable in PEMFC cathode applications wheremaximum exposure of oxygen and effectively removing water are criticalto the cell performance. To circumvent such issues, nanostructuredmaterials, such as functionalized carbon nanotubes, have been evaluatedas non-PGM catalyst to improve the mass/electron transports. Forexample, it has been demonstrated that Fe/N decorated aligned carbonnanotube could serve as the electrode catalyst for PEMFC. To decoratecarbon nanotube (CNT) with a non-PGM catalytic site either throughdirect synthesis or via post-addition has some significant limitations.For example, a chemical vapor deposition (CVD) step is typically usedfor direct synthesis of CNT. The CVD mixture must to be vaporized firstbefore decomposition during the CNT formation. Such a requirement limitsthe types of precursors that can be used to functionalize CNT.Furthermore, forming active site through nanotube growth is not aneffective method of integrating high concentration atomic nitrogen intothe graphitic layer as part of the catalytic center therefore cannotbuild highly active catalyst. Adding N-containing transition metalorganometallic compound on the preformed CNT surface is another approachto fabricate the catalyst with nano-tubular structure. Such a compoundcan only be applied on the outer surface of the CNT which again limitsthe density of the catalytic active site. Furthermore, only theorganometallic compounds soluble to the solvent compatible to the CNTcan be used in such approach, which again greatly limits the choice ofthe precursors in improving the catalytic performance.

For the LAB application, ORR and OER occur over the cathode surfaceduring discharging and charging step, respectively. At present, variouscatalysts including transition metal oxide and precious metals have beenused and supported by the carbon materials. Such carbons can beamorphous or graphitic, but in general are randomly agglomerated withoutordered nano-architecture. Since the cathode reactions in LAB occurbetween the interfaces of liquid electrolyte, solid catalyst and gaseousoxygen, maximal mass transfer and interaction are difficult to establishthrough such a random arrangement, which is similar to the cathodicprocess in PEMFC. In addition, solid precipitates such as lithium oxidesare expected to form and decompose during discharge/charge cycle. Suchprecipitates can be deposited over the exterior surface of the carbonsupport, blocking the pores and thereby the access of electrolyte andoxygen into the catalysts inside of the pores. Consequently, manyproblems remain to be solved.

SUMMARY OF THE INVENTION

A method is provided for preparing a new class of electrode catalyst topromote the oxygen reduction reaction and oxygen evolution reaction atthe cathode of a PEMFC or LAB. These electrode catalysts are preferablyin the form of fabric structures containing a low level of transitionmetal and nitrogen embedded in a carbon fiber matrix. Alternatively, thestructure contains a transition metal oxide evenly dispersed over thecarbon fiber matrix. The carbon fibers are in the nanometer dimensionrange and can be solid or hollow, with optional holes on the surface.Such nanofibrous electrode catalysts have advantages of promoting masstransport between the reactant and catalyst site through a porousframework. The catalyst also improves thermal and electronic transfersthrough carbon fiber network with minimum percolation inducedresistance. They also can enhance catalyst stability against oxidativecorrosion through graphitic and low space curvature support and alsoreduce the cost by eliminating the usage of precious metal material. InPEMFC applications, such catalytically functionalized fibers can serveas the cathode catalyst to promote the oxygen reduction reaction andwith high current density and durability. In LAB applications, suchcatalysts can also improve efficiency by reducing charge/dischargeoverpotentials and cycling stability.

One advantageous aspect of the current invention is the formulation ofthe electrospinning precursor solution for the production of a low cost,nanofibrous electrode catalyst. The compositions include transitionmetal compounds, either in the form of organometallics, metal organicframework or inorganic salt, with an optional organic ligand forchelating, the soluble fiber forming polymer and solvent with metal. Allthe components are mixed into a solution, and such solutions aresuitable to fabricate nano-fibers through an electro-spinning approach.

Another aspect of the current invention is the formulation of theelectrospinning precursor solution for the production of a porousnanofibrous electrode catalyst. The compositions include transitionmetal compounds, either in the form of organometallics, metal organicframework, inorganic salt or metal oxide, with an optional organicligand for chelating with metal, and placing the soluble fiber-formingpolymer, solvent, and pore-forming reagent into a solution. All thecomponents are mixed into a solution and such a solution is suitable tofabricate porous nano-fiber through the electro-spinning approach.

Yet another aspect of the current invention is to produce thenano-fibers from the precursor solution using an electro-spinningmethod. The nanofibers are generated under a controlled electric fieldbetween the injector nozzle and collector plate and a controlledinjection feed-rate.

A further aspect of the current invention is to thermally activate theprepared nanofibers to convert them from polymeric to carbonaceousmaterials through a high temperature treatment, such as pyrolysis in aninert or reducing atmosphere. Such a treatment leads to decomposition oftransition metal compounds and nitrogen containing organic compounds;and reactions between different components within the mixture form thecatalytic active site on the nanofibers. Such a treatment will alsogenerate additional pores around nanofibers after decomposing thepore-forming reagent and further produce a higher surface area andexposure of the catalytic site. Furthermore, such an activation processwill also improve the electronic conductivity because it converts theorganic components to more conductive carbonaceous material which isimportant for the electrode catalyst.

An additional aspect of the current invention is to further processthermally activated nanofibers with the post-treatment methods includingan acid wash, ball milling and second thermal treatment in the inert gasor in the presence of ammonia. Such a post-treatment method can furtherenhance the catalyst activity.

Another aspect of the current invention is to prepare a cathode layer ofa membrane electrode assembly (“MEA”) using ink mixed with the activatednanofiber as catalyst, which can be an ion-conducting polymer solution,such as Nafion ionomer solution. Such an MEA can be assembled in a PEMFCto convert chemical energy to electric energy.

A further aspect of the current invention is to prepare a catalyst layerusing ink mixed with the activated nanofiber with or without transitionmetal oxide as a catalyst and a polymer binder. Such a catalyst layercan be used as the cathode in a rechargeable LAB.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a process flow chart for preparing nanofibrous non-PGMelectrode catalyst for PEM fuel cell and the lithium-air batteryapplications;

FIG. 2 shows a schematic drawing of the electro-spinning set-up forproducing non-PGM electrode catalyst for PEM fuel cell and thelithium-air battery applications;

FIG. 3 shows a scanning electron microscopic image of the polymericnanofiber according to Example 2;

FIG. 4 shows a polarization curve of cell voltage (E_stack) and cellpower density as the function of cell current density (I) measuredaccording to the experiment described by Example 3;

FIG. 5 shows a scanning electron microscopic image of the carbonizednanofibrous electrode catalyst obtained according to the description inExample 4;

FIG. 6 shows a polarization curve of cell voltage (E_stack) and cellpower density as the function of cell current density (I) measuredaccording to the experiment described by Example 6;

FIG. 7 shows normalized current densities (at 0.5 V) as the function ofcycle number in a side-by-side comparison between a PEMFC with thenanofibrous catalyst according to the current invention and a commercialPt/C catalyst, as described by the description in Example 7;

FIG. 8 shows a scanning electron microscopic image of the carbonizednanofibrous electrode catalyst obtained according to the description inExample 8; and

FIG. 9 shows the cell voltage as the function time in a multiple cycledischarge-charge test of a lithium-O₂ battery using nonfibrous cathodeaccording to Example 9.

FIG. 10 shows one embodiment of a fuel cell membrane electrode assembly.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In a preferred method of the invention nitrogen- and carbon-containingnanofibrous electrode catalysts are prepared by embedding with atransition metal or transition metal oxide, but free of platinum groupmetals. The materials are prepared according to the process flow chartshown in FIG. 1, and as described by the following steps; I) preparingthe precursor solution containing transition metal based activeingredient, either in soluble form or solid, fiber-forming polymer,optional pore-forming polymer, and solvent; II) forming nanofibers usingthe electrospinning method with the precursor solution prepared in stepI; III) converting the nanofibers from non-active polymeric form to acatalytically active carbonaceous form through heat-treatment atelevated temperature; and IV) further improving electrocatalyticactivity of the nanofibrous catalysts from step III with additionalchemical treatment. The details of each step are described hereinafter:

Preparing a precursor solution mixture in step I, according to oneembodiment of the current invention, involves use of a precursorsolution which preferably contains three components: the catalyticprecursor that can be converted to catalytic active site after thermaltreatment, a polymer to form the backbone of the nanofibrous carbonafter activation, an optional polymer to form nanopores over thenanofiber, an optional organic ligand to coordinate with the transitionmetal to new metal-ligand complex in the precursor solution, and asolvent for mixing the catalytic precursor and the polymer. Oneparticular advantage of an electro-spinning approach in this embodimentis the flexibility of incorporating a broader range of the catalyticprecursors in the electro-spinning solution. For example, the catalyticprecursors could be completely soluble in the electrospinning solution.Alternatively, they could also be present as a suspended solid. Thesoluble catalytic precursors include the transition metal organometalliccompounds or salts that can be dissolved in the solvent, such asmetalloporphyrin, metallo-phthalocyanine, metallocene,metallo-phenanthroline complexes, metal acetate, metal nitrate, andmetal chloride. Some specific examples include iron porphyrin, cobaltporphyrin, iron phathlocynine, cobalt phathalocine, ferrocene,cobaltacene, 1,10-phenanthroline iron(II) perchlorate, iron acetate,cobalt acetate, manganese acetate, iron nitrate, manganese nitrate,cobalt nitrate, iron chloride, cobalt chloride, and manganese chloride.The insoluble, solid catalytic precursors include transition metalorganic frameworks. Some specific examples include iron zeoliticimidazole framework (Fe-Im), cobalt zeolitic imidazole framework(Co-Im), iron zeolitic methyl-imidazole framework (Fe-mIm), cobaltzeolitic methyl-imidazole framework (Co-mIm), zinc zeolitic imidazoleframework (Zn-Im), zinc zeolitic methyl-imidazole framework (Zn-mlm),and zinc zeolitic ethyl-imidazole framework (Zn-eIm). An optionalnitrogen-containing organic ligand can also be added into the precursorsolution to form new metal complex through metal-nitrogen ligation bondwhen reacts with soluble transition metal compounds. Some examples oforganic ligand include bi-pyridine, aniline, porphyrin, phathlocynine,phenanthroline, and the like. The polymer components in the mixtureinclude the first polymer that can form the fibrous backbone; and theoptional second polymer that can generate pores during thermalactivation. For example, the fibrous backbone forming polymers includepolyacrylonitrile (PAN), polycarboate (PC), polybenzimidazole (PBI),polyurethanes (PU), Nylon6,6, polyaniline (PANT), polycaprolactone(PCL), and others well known in the art. The pore forming polymersinclude polymethylmethacrylate (PMMA), polyethylene oxide (PEO), andothers well known in the art. The solvents used for the mixturepreparation include those which can dissolve the soluble catalyticprecursors and the polymers. Examples include dimethyl formamide (DMF),dimethylamine (DMA), N-Methyl-2-pyrrolidone (NMP), methylene chloride,methanol, ethanol, propanol, and acetone. In a preferred embodiment, thesoluble catalytic precursors can include iron acetate, manganeseacetate, iron porphyrin, and 1,10-phenanthroline iron(II) perchlorate;and the insoluble precursors include Zn-mlm, Zn-elm, Fe-mlm, and Co-mlm.Also in a preferred embodiment, the fibrous backbone forming polymerincludes PAN and the pore-forming polymer can include PMMA. Also in thepreferred embodiment, the solvent can include DMF. All the components inthe precursor mixture should first be preferably mixed uniformlytogether before the electro-spinning step. For the soluble catalyticprecursors, the precursor and the polymers are preferably the firstcomponents to be completely dissolved by the solvent. For the insolublecatalytic precursors, the polymers are first preferably dissolved by thesolvent followed by addition of the precursor. Mechanical means, such asball-milling and blending, may be needed to break down the solidparticles and to produce the mixture where the micro-particle solid canbe suspended in the solution during the electro-spinning process.

In step II, electro-spinning method is preferably used to producenanofibers. The electro-spinning method is well known in the art, and aschematic diagram of an apparatus 100 is shown in FIG. 2. Generally, theapparatus includes a syringe pump 110 with an injection needle 120 madeof electro-conductive material such as metal, a high-voltage directcurrent (DC) power supply 130 and a collector plate 140 made ofconductive substrate such as stainless steel or carbon paper. During theelectro-spinning process, a precursor solution droplet is formed at thetip of an injection needle 120 as the syringe pump 110 pushes themixture out. Under application of high voltage, the liquid drop becomescharged and is stretched by an electric field between and needle 120 andthe collector plate 140 forming a liquid jet. As the liquid jet fliesfrom the needle 120 to the collector plate 140 under the continuouselongation, thinning and drying, the polymeric nanofiber is formed anddeposited on the collector plate 140. In our preferred experimentalconditions, the injection needle has the gauge size of twenty, theinjection rate is generally controlled at 4 microliter/min, and theelectric field is generally set at 1 kV/cm. Both carbon paper andstainless steel sheets are used as the fiber collector plates 140.

In step III, a heat treatment is used to treat the polymeric nanofibersproduced from step II. The heat treatment converts the catalyticprecursor to the catalytic center, converts polymeric nanofiber tographitic nanofiber and generates micropores by decomposing pore-formingcomponents. Not limiting the scope of the invention, the heat treatmentwill initiate the reaction between the catalytic precursor components inthe nanofiber and leading to the formation of catalytic active sitescontaining nitrogen embedded in the graphitic crystallites of thenanofiber. Alternatively, the heat treatment could also convert themetal salt to metallic crystallite, which will later be converted tometal oxide supported by the nanofiber when it exposed to air. Thethermal treatment will also convert the polymeric fiber to graphiticfiber therefore significantly increasing the electric conductivity whichis crucial for the electrochemical reaction. In the case of PAN, forexample, the polyacrylonitrile will undergo H and N elimination duringthe conversion to a graphitic fiber. Another benefit of heat-treatmentis to produce the porosity throughout the fiber to thereby improve theinteraction between the reactant and the catalytic sites inside of thefiber core. The pore forming can be achieved through eitherdecomposition of polymer additive or vaporization of volatile solidcomponents at elevated temperatures. In the case of a pore formingpolymer, the decomposition to smaller, volatile fragments occurs throughchain-scission and the porosity is generated by the escaping gaseouscomponents under the high temperature. For example, the pore-formingpolymer PMMA can be broken down to its monomer fragments during heatingto produce pores throughout the nanofiber backbone. Another route offorming porosity is through the decomposition of the volatile solidcomponent under elevated temperatures. For example, when metal organicframework Zn-mIm or Zn-eIm is used as the precursor component, the ionicZn will be first reduced to metallic zinc before vaporizing at slightlyabove 900° C., leaving micropores through the body of the nanofiber. Thethermal conversion of the polymeric nanofiber is generally conducted ina controlled environment, such as a sealed reactor or a flow reactorsurrounded by a heating element (not shown). In a preferred embodiment,the treatment consists of two segments and is carried out inside of atubular reactor under the constant flow of carrier gas surrounded bytemperature controlled furnace. The first segment represents the thermalcure of the polymeric nanofibers. The treatment occurs usually in air orinert environment with temperature up to about 300° C., and the durationof treatment is between about one to 24 hours. In a preferredembodiment, the temperature is in the range of 150 to 200° C. with theduration of about 4 to 10 hours. Not limiting the scope of theinvention, such treatment can lead to crosslinking and pore formingreaction of the polymeric media of the fiber. The second segmentinvolves the thermal conversion at a temperature typically ranging fromabout 600° C. to 1100° C. In a preferred embodiment, the temperatureranges from about 700° C. to 1050° C. The time for which the sample isat the thermal conversion temperature should also preferably becontrolled. According to a preferred embodiment of the invention, thethermal treatment time should also be controlled to be between about 20minutes to 3 hours. In the most preferred embodiment, the time under thetreatment of temperature should be about 20 minutes to 90 minutes.Another condition for thermal treatment that can be controlled is thechemical composition of the carrier gas. In one embodiment of theinvention, the carrier gas should be inert gases such as Ar or He, or tosome degree, lesser inert gases such as nitrogen. In another embodimentof the invention, the carrier gas should be reductive and containingnitrogen. The examples of such a reducing carrier gas include, but arenot limited to, ammonia, pyridine, and acetonitrile. Not limiting thescope of the invention, the carrier gas containing nitrogen can alsopromote addition of nitrogen to the graphitic fiber during thermaltreatment thus increase the number of potential active sites.

In step IV, a post treatment process is performed. After the thermalconversion process in step III, the nanofibrous material can beprocessed through a post-treatment step to further improve theelectrocatalytic activity. According to one embodiment, a post-treatmentmethod can be accomplished through acid washing. A variety of inorganicacids can be used to dissolve the excess amount of TM in the materialfrom step III by simply immersing the thermally treated nanofiber in theacid solution. The acids include hydrochloric acid, sulfuric acid,nitrate acid, and other acids known to dissolve metals. Theconcentration of the acid can be in the range of about 0.1 molar toundiluted concentrations. In a preferred embodiment, the concentrationof the acid ranges from about 0.5 molar to 2 molar. The acid treatmenttemperature can range from ambient to as high as about 80° C. The acidtreatment time ranges from about 0.5 hour to 12 hours. In anotherembodiment of the current invention, the acid washed material can befurther treated under elevated temperature in an inert gas flow or in aflow of nitrogen-containing gas such as ammonia under the similartemperature and carrier gas condition described in step III. Such asecond thermal treatment can further improve the electrocatalyticactivity. In yet another embodiment of the invention, the post-treatmentinvolves reapplying a nitrogen-containing ligand and the transitionmetal organometallic compounds as described by step I to the thermallytreated nanofiber produced from step III. This is then followed byanother thermal treatment based on the procedure described in step III.Such a second heat treatment enables the addition of more active site tothe carbon fiber and thus obtaining higher catalytic activity. In yetanother embodiment of the invention, the graphitic nanofiber containingmetallic crystallites from step III can be subjected to low-temperatureheating in the presence of flowing air or oxygen so that the metalcrystallites will be converted to metal oxide which can serve as thecatalyst for LAB applications. The treatment temperature is typicallyfrom about 50° C. to 200° C.

FIG. 10 shows one embodiment of a fuel cell membrane electrode assembly(MEA). The MEA includes an anode 810 and a cathode 820 with a fuel cellmembrane 830 therebetween. The cathode comprises a carbon papersubstrate loaded with a catalyst ink comprising an ionomer solution withcatalytic powder mixed therein, the catalytic powder having a pluralityof graphitic nanofibers and catalytically active metal moieties andnanopores throughout.

The process of preparing nanofibrous electrocatalyst according to theembodiments of the current invention can be further elucidated by thefollowing non-limiting examples.

Example 1

A precursor solution was prepared according to the following steps: Apolymer mixture of PMMA and PAN in the weight ratio of 1.5:1 was firstdissolved in the excess of DMF (×8 by weight) as the solvent to formsolution 1. Separately, polymer PANI was dissolved in solvent DMF in theweight ratio of 1:20 to form solution 2; and 1,10-phenanthrolineiron(II) perchlorate was dissolved into DMF in the weight ratio of 1:20to form solution 3. The solutions 1, 2 and 3 were then mixed together inthe volume ratio of 5:3:1 to form the final precursor solution. Theprecursor solution thus formed was electrospun to the polymericnanofibers under an applied voltage of 1 kV/cm. A representative imageof the polymeric nanofiber is shown in FIG. 3. The nanofibers thusprepared were subsequently transferred to a calcination dish andsubjected to the heat-treatment. The heat treatment consisted of thefollowing steps; the sample was heated in flowing air at 200° C. for 8hours before the second step of heating in flowing Ar at 1000° C. forone hour. The temperature was subsequently reduced to 820° C., and thesample was exposed to flowing ammonia for anther 10 minutes beforeretuning to the room temperature. After the heat treatment, the samplewas transferred to 0.5 M H₂SO₄ and sonicated for 30 min to wash away theexcess elemental iron. After the acid wash, the sample was dried andtreated again in flowing ammonia for 20 minutes at 800° C.

Example 2

The nanofibrous catalyst prepared according to Example 1 was made intothe cathode of a fuel cell membrane electrode assembly (MEA). A catalystink was first prepared by mixing the catalyst powder from Example 1 witha Nafion ionomer solution so that the weight ratio of the catalyst toNafion was 1:1. The ink was subsequently sprayed over a carbon paper (5cm², Avcarb), which was then heated under vacuum at 80° C. for 1 hour.The catalyst loading after drying was 1.8 mg cm⁻². For the anode, an inksolution containing Pt/C (20 mg, 20 wt % of Pt, BASF), Nafione (5 wt %solution, Aldrich,), ethanol and water was sonicated for 1 hour andstirred for 0.5 hour, and then sprayed onto a carbon paper (5 cm²,Avcarb), which was then heated under vacuum at 80° C. for 1 hour. The Ptloading was 0.5 mg cm⁻². The prepared cathode and anode were thenpre-pressed against either side of a Nafion® 211 membrane (DuPont) at120° C. for 1 minute using a load of 500 lb. The pre-pressed assemblywas then hot-pressed at 120° C. for 2 minutes using a load of 1000 lb toyield the final MEA for a single cell polarization test.

Example 3

The MEA prepared according to Example 2 was installed in a fuel celltest station (Scribner 850e), and the cell performance was evaluated.The fuel cell test was carried out using a single cell with serpentineflow channels, and a geometric electrode surface area of 5 cm². UHPgrade gases were used. During the test, the cell temperature was kept at80° C. Gases were humidified at 80° C. and were kept at a constant flowrate of 0.3 L min⁻¹ for H₂ and 0.4 L min⁻¹ for O₂, respectively. Thetotal pressure was set at 22 psig for both anode and cathode. Shown inFIG. 4 is the polarization curve of cell voltage (E_stack) as a functionof cell current density (I) and was obtained by scanning the cellcurrent from 0 to maximum at a scan rate of 1 mA s⁻¹. In the same chart,the power density, which is the product of the cell voltage and currentdensity, was also plotted.

Example 4

A precursor solution was prepared according to the following steps; Apolymer mixture of PMMA and PAN in the weight ratio of 1:1 was firstdissolved in the excess of DMF (×16 by weight) as the solvent to formsolution 1. Separately, a zinc based zeolitic imidazole framework, ZIF-8was added as a suspended solid in DMF in the weight ratio of 1:20 toform solution 2; and 1,10-phenanthroline iron(II) perchlorate wasdissolved into DMF in the weight ratio of 1:20 to form solution 3. Thesolutions 1, 2 and 3 were then mixed together in the volume ratio of8:4:1 to form the final precursor solution. The precursor solution thusformed was electrospun to form the polymeric nanofibers under an appliedvoltage of 1 kV/cm. The nanofibers thus prepared were subsequentlytransferred to a calcination dish and subjected to the heat-treatment.The heat treatment consisted of the following steps: the sample washeated in flowing air at 200° C. for 8 hours before the second step ofheating in flowing Ar at 1000° C. for one hour. The temperature wassubsequently reduced to 900° C., and the sample was exposed to flowingammonia for anther 10 minutes before retuning to the room temperature.After the heat treatment, the sample was transferred to 0.5 M H₂SO₄ andsonicated for 30 min to wash away the excess elemental iron. After theacid wash, the sample was dried and treated again in flowing ammonia for30 minutes at 700° C. A representative image of the carbonized nanofiberis shown in FIG. 5.

Example 5

A catalyst ink was first prepared by mixing the catalyst powder fromExample 4 with a Nafion ionomer solution so that the weight ratio of thecatalyst to Nafion was 1:1. The ink was subsequently sprayed over acarbon paper (5 cm², Avcarb), which was then heated under vacuum at 80°C. for 1 hour. The catalyst loading after drying was 1.8 mg cm⁻². Forthe anode, An ink solution containing Pt/C (20 mg, 20 wt % of Pt, BASF),Nafion® (5 wt % solution, Aldrich,), ethanol, and water was sonicatedfor 1 hour and stirred for 0.5 hour, and then sprayed onto a carbonpaper (5 cm², Avcarb), which was then heated under vacuum at 80° C. for1 hour. The Pt loading was 0.5 mg cm⁻². The prepared cathode and anodewere then pre-pressed against either side of a Nafion® 211 membrane(DuPont) at 120° C. for 1 minute using a load of 500 lb. The pre-pressedassembly was then hot-pressed at 120° C. for 2 minutes using a load of1000 lb to yield the final MEA for the single cell polarization test.

Example 6

The MEA prepared according to Example 5 was installed in a fuel celltest station (Scribner 850e) and the cell performance was evaluated. Thefuel cell test was carried out using a single cell with serpentine flowchannels and a geometric electrode surface area of 5 cm². UHP gradegases were used. During the test, the cell temperature was kept at 80°C. Gases were humidified at 80° C. and were kept at a constant flow rateof 0.3 L min′ for H₂ and 0.4 L min⁻¹ for 02, respectively. The totalpressure was set at 22 psig for both anode and cathode. Shown in FIG. 6is the polarization curve of cell voltage (E_stack) as the function ofcell current density (I) and was obtained by scanning the cell currentfrom 0 to maximum at a scan rate of 1 mA In the same chart, the powerdensity, which is the product of the cell voltage and current density,was also plotted.

Example 7

An MEA prepared in a similar method according to Example 5 was testedside-by-side with a commercial Pt based MEA (BASF, P.O. 9A-31427). BothMEAs were installed in single cell test assemblies and subjected to themultiple cycling aging test. The cycling condition included flowing 4%H₂ in He at anode and nitrogen at cathode and both were humidified at80° C. and kept at a constant flow rate of 0.2 L min⁻¹. Shown in FIG. 7are the normalized current densities (at 0.5 V) for both cells testedintermittently during the multicycle aging. As one can see, thenormalized current density of the MEA with nanofibrous non-PGM cathodedecayed slower than that of commercial Pt MEA up to 15000 cycles.

Example 8

A precursor solution was prepared according to the following steps; Apolymer mixture of PMMA and PAN in the weight ratio of 1:3 was firstdissolved in the excess of DMF (×16 by weight) as the solvent to formsolution 1. Separately, a zinc based zeolitic imidazole framework, ZIF-8was added as the suspended solid in DMF in the weight ratio of 1:20 toform solution 2; and 1,10-phenanthroline iron(II) perchlorate wasdissolved into the DMF in the weight ratio of 1:20 to form solution 3.The solutions 1, 2 and 3 were then mixed together in the volume ratio of13:5:1 to form the final precursor solution. The precursor solution thusformed was electrospun to form the polymeric nanofibers under theapplied voltage of 1 kV/cm. The nanofibers thus prepared weresubsequently transferred to a calcination dish and subjected to theheat-treatment. The heat treatment consisted of the following steps; thesample was heated in flowing air at 200° C. for 8 hours before thesecond step of heating in flowing Ar at 1000° C. for one hour. Thetemperature was subsequently reduced to 900° C., and the sample wasexposed to flowing ammonia for another 10 minutes before returning tothe room temperature. The SEM image of nanofibers thus prepared is shownin FIG. 8.

Example 9

The nanofibrous cathode catalyst prepared according to Example 8 wasfabricated into a LAB cathode. Two pieces of catalyst films withdiameter of 7/16″ were used as cathode. The loading of catalysts andcarbons were between 0.6 mg. Li foil was used as the anode, and acircular porous glass fiber filter (Whatman, ½″ in diameter) was used asthe separator. Electrolyte was 1 M LiCF₃SO₃ (99.995% pure) intetraethylene glycol dimethyl ether (TEGDME) (Aldrich). LiCF₃SO₃ wasdried in vacuum oven in a glovebox before using. Analytical grade TEGDMEwas treated by distillation and molecular sieve before using. Bothelectrodes and the separator were stacked into a half inch Swagelokunion, which was placed inside of a sealed glass cell. For a cyclingtest, the glass cell was filled with oxygen accessible to the cathodelayer through an open-end connector. The discharge/charge cycling wascontrolled by a MACCOR system under a constant current of 0.05 mA withlimited duration of 5 hours for single discharge and charge. Cut-offvoltage limits were 2.3 V for discharge and 4.4 V for charge. FIG. 9shows the cell voltage as the function of time in a multiple cycledischarge-charge cell test.

The electrode catalysts prepared in accordance with the method of theinvention have several advantages over that of prior art in thefollowing aspects, including improved mass transfer and humiditymanagement. The preferred nanofibrous catalyst according to the currentinvention contains selected levels of micro-, meso- and macropores inits architecture. Compared with amorphous carbon structures reported bythe prior art, the instant nanofibrous morphology enables efficienttransfer of gas reactants to the entire thickness of the cathode layer,which thereby improves the catalyst site utilization through betterinteraction with the oxygen in both PEMFC and LAB. In PEMFC, water isproduced through the reaction between the proton and the reduced oxygen.Effective removal of additional water is critical for stable fuel celloperation since the cathode surface can be flooded by the excess ofmoisture, which is often observed in the case of an amorphous carbonstructure used in the prior art. Unlike the prior art, the instantnanofibrous catalyst structure according to the current invention,however, has high porosity and connectivity between different poreswhich therefore can mitigate water built-up by the effective penetrationof cathode gas flow at all thickness level.

The nanofibrous catalyst has other advantages, including two intrinsicadvantages in catalyst stability. As previously described, the backboneof the nanofibrous catalyst is a graphitic fiber produced by carbonizinga polymer over a temperature preferably of about 1000° C. Graphiticfiber is known to be significantly more tolerant than amorphous carbonto the oxidative environment in the PEMFC or LAB cathode. Therefore, itcan better preserve the electrode integrity under corrosive conditions.The graphitic skin of the nanofiber also provides a protective layerover the catalytic active site and hence can extend the cathodedurability. Furthermore, the nanofibrous catalyst has a smooth fibercurvature with a diameter in the tens to hundreds of nanometers. Suchlarge and smooth curvature is more resistant to the oxidative corrosionthan that of amorphous carbons of smaller particle size with highlyreactive unsaturated or oxidized edges.

Other advantageous features include the nanofibrous catalyst having aform of continuous, interconnected graphitic fibrous framework, and thusit offers significantly better electronic and thermal conductivity thanknown amorphous counterparts which conduct electron/heat throughpercolation between individual carbon particles. Such percolation inknown systems can be easily interrupted when carbon particles shrinktheir dimensions by oxidative loss. On the contrary, the connectivity ofthe nanofibers will not be significantly affected even if the fiberdiameter is reduced slightly by oxidation.

In another advantageous aspect, the method and system described hereinoffers significantly greater flexibility over known catalysts by using avariety of precursors to incorporate the catalytic active sites. Unlikethe carbon nanotube in which the active center is formed through thechemical vapor deposition technique with only limited transition metaland nitrogen-containing precursors, the method herein for manufactureand the resulting article can integrate numerous different precursors,either soluble or insoluble by the solvent, into the precursor mixturebefore converting them into nanofibers. The metal or N-containingprecursors do not need to be vaporized to form the nanofiber catalyst.Therefore, the current method and article of manufacture has theadvantage of using a broad selection of the catalytic precursor withmore flexibility in catalyst design and resulting activity improvement.

The foregoing description of embodiments of the present invention havebeen presented for purposes of illustration and description. It is notintended to be exhaustive or to limit the present invention to theprecise form disclosed, and modifications and variations are possible inlight of the above teachings or may be acquired from practice of thepresent invention. The embodiments were chosen and described in order toexplain the principles of the present invention and its practicalapplication to enable one skilled in the art to utilize the presentinvention in various embodiments, and with various modifications, as aresuited to the particular use contemplated.

What is claimed is:
 1. An article of manufacture of a catalyst,comprising: a nanofibrous continuous network of graphitic nanofibershaving catalytically active metal moieties embedded within the graphiticnanofibers and the graphitic nanofibers having a matrix ofinterconnected nanopores exposing the catalytically active metalmoieties, wherein a graphitic skin of the graphitic nanofibers providesa protective layer over the catalytically active metal moieties embeddedwithin the graphitic nanofibers.
 2. The article of manufacture asdefined in claim 1, wherein the catalyst forms a component selected fromthe group of a cathode in PEMFC membrane electrode assembly and acathode of a lithium air battery.
 3. The article of manufacture asdefined in claim 1, wherein the metal moieties originate from aprecursor having composition comprising transition metal zeoliticimidazolate frameworks comprising iron zeolitic imidazole framework(Fe-Im), cobalt zeolitic imidazole framework (Co-Im), iron zeoliticmethyl-imidazole framework (Fe-mIm), cobalt zeolitic methyl-imidazoleframework (Co-mlm), zinc zeolitic imidazole framework (Zn-Im), zinczeolitic methyl-imidazole framework (Zn-mlm), or zinc zeoliticethyl-imidazole framework (Zn-elm).
 4. The article of manufacture ofclaim 1, wherein the catalytically active metal moieties comprisecatalytically active transition metal, nitrogen and carbon moieties. 5.The article of manufacture of claim 1, wherein the catalytically activemetal moieties comprise catalytically active metal oxide compoundcrystallites.
 6. The article of manufacture as defined in claim 1,wherein the graphitic nanofibers have a diameter of about ten nanometersto one thousand nanometers.
 7. The article of manufacture of claim 1,wherein the graphitic nanofibers comprise a thermally carbonizedbackbone forming polymer and a carbonized pore forming polymer.
 8. Thearticle of manufacture of claim 7, wherein the backbone forming polymeris carbonized to graphitic form.
 9. The article of manufacture of claim8, wherein the graphitic nanofibers have crosslinking therebetween. 10.A cathode comprising: a carbon paper substrate; and a dried catalyst inkcomprising a plurality of graphitic nanofibers having catalyticallyactive metal moieties embedded within the graphitic nanofibers and thegraphitic nanofibers having a matrix of interconnected nanoporesthroughout exposing the catalytically active metal moieties, wherein thedried catalyst ink is disposed on the carbon paper substrate, wherein agraphitic skin of the graphitic nanofibers provides a protective layerover the catalytically active metal moieties embedded within thegraphitic nanofibers.
 11. The cathode of claim 10, wherein thecatalytically active metal moieties comprise catalytically activetransition metal, nitrogen and carbon moieties.
 12. The cathode of claim10, wherein the catalytically active metal moieties comprisecatalytically active metal oxide compound crystallites.
 13. The cathodeof claim 10, wherein the graphitic nanofibers comprise a thermallycarbonized backbone forming polymer and a carbonized pore formingpolymer.
 14. The cathode of claim 10, wherein the graphitic nanofibershave crosslinking therebetween.
 15. A fuel cell membrane electrodeassembly comprising: an anode; a cathode comprising: a carbon papersubstrate; and a dried catalyst ink comprising a catalytic powder havinga plurality of graphitic nanofibers and catalytically active metalmoieties embedded within the graphitic nanofibers and the graphiticnanofibers having a matrix of interconnected nanopores exposing thecatalytically active metal moieties, and a fuel cell membrane having theanode and cathode pressed into the fuel cell membrane, wherein agraphitic skin of the graphitic nanofibers provides a protective layerover the catalytically active metal moieties embedded within thegraphitic nanofibers.
 16. The fuel cell membrane electrode assembly ofclaim 15, wherein the catalyst ink has a dry catalyst loading of 1.8mg/cm² on the carbon paper substrate.
 17. The fuel cell membraneelectrode assembly of claim 15, wherein the catalytically active metalmoieties comprise catalytically active transition metal, nitrogen andcarbon.
 18. The fuel cell membrane electrode assembly of claim 15,wherein the catalytically active metal compound crystallites comprisecatalytically active metal oxide compound crystallites.
 19. The fuelcell membrane electrode assembly of claim 15, wherein the graphiticnanofibers comprise a thermally carbonized backbone forming polymer anda carbonized pore forming polymer.